Co-nhxnh-



United States Patent FUNGICIDFS Ewnld Urbschat, Koln-Mnlheim, and Paul-Ernst Frohherger, Burscheid, Bezirk Dusseldorf, Germany, asslgnors to Farbenfabrlken Bayer Alrtiengesellschaft, Leverlrusen, Germany, a corporation of Germany No Drawing. Original No. 2,911,336, dated Nov. 3, 1959, Ser. No. 535,513, Sept. 20, 1955. Application for reimue July 28, 1960, Ser. No. 46,042

Claims priority, application Germany Sept. 24, 1954 8 Claims. (Cl. 167-30) Matter enclosed in heavy brackets [1 appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

The present invention relates to useful improvements in fungicides; more particularly it is concerned with compounds of the type embraced by the general formula which are useful in rendering seed grain immune against attacks by fungi.

Good results have been obtained in controlling, by seed dressing, a number of plant diseasescaused by micro-organisms, which adhere to the seeds and are spread with the seeds. The phyto-pathogenic fungi which can be controlled by seed dressing include Tilletia tritici, Ustilago avenae, Helminthosporium gramineum, Fusarium nievale, Ustilago hordei, and Phoma betae.

Among the customary seed dressing agents, the preparations having a basis of organic mercury compounds, which are highly efiective in formulations containing only i few percent of the active substances, play the most important part. Such preparations show any outstanding eflicaey and kill the organisms on the seeds practically completely. As compared with these highly efiective mercury dressing agents, other preparations containing metal-free active substances are of secondary importance since they have to be applied at a higher concentration, which renders them uneconomic to agriculture, or they fail to show a universal activity.

Apart from certain toxicological deficiencies, the previously known highly effective mercury disinfectants sufler from a considerable disadvantage which is due to the fact that only the surface of the seeds and the soil surrounding same within a radius of 1-2 mm. can be. disinfected therewith and the seedling growing out of Reissued Apr. 4,

diseases on various plants, such as leguminous plants, beet, maize, flax and cotton (for imtance damping-off, seedling blight, pied noir, fonte de semis), which diseases lead to considerable losses to agriculture. Such germination diseases impair the crop yields either by reducing the number of plants or delaying their development process. Besides, these germination diseases frequently require resowing which involves additional cost and delay in the development process. Damages to crops due to germination diseases especially result when the germination and the shooting-up of the seeds are delayed by unfavorable conditions so that the seedlings, for a long time, retain their initial stages of growth during which they are especially predisposed to diseases. Shooting and germination are retarded in particular by low ground temperatures after sowing and adverse structure of the soil.

Whereas the mercury seed dressings formerly used are insufliciently effective against certain disease-carrying organisms, it has recently been found that such diseases can be decisively reduced by treatment with quinone oxime acyl hydrazones. These agents are not only eflective against the organisms on the surface of the seeds and in the narrowly confined spermatosphere but, moreover, also protect the sprout and the root of the seedlings against certain fungicidal infections from the soil.

A large number of these compounds, which are described for instance in French Patent 1,093,364, have proved to be excellently eflective as seed dressing agents against germination diseases. The superiority over organic mercury compounds is demonstrated by their capacity of eliminating infections originating from the soil to a substantially larger extent; besides, the desired efiect can be reached with concentrations below the mercury proportions in mercury-containing disinfectants. Other metal-free substances which have been proposed as disinfectants against the same diseases require still higher concentrations in the disinfectants.

The principal object of the present invention is to provide a class of compounds having a strong fungicidal activity. Further objects will become apparent from the following description.

In accordance with the present invention it has been found that compounds of the general formula bacteria causing germination diseases. They are even this narrowly restricted spermatosphere is subject to attack by phyto-pathegenic soil-borne fungi.

A great variety of soil-borne fungi, such as Pythium debaryanum, Aphanomyces laevis, Phymatotrichum omnivorum, and Rhizoctonia solani, cause germination efi'ective against seed-borne diseases which are diflicultto control by means of metal-free disinfectants and show an outstanding efiect particularly against germination diseases of plan-ts, beet, maize, flax and cotton. Inthis respect, they are not only far superior to the previously known metal-free compounds hitherto used in the con- 60 trol of these diseases, such as tetra-methyl-thiuram-disul- ,p-arninophenyl-p-chlorobenzoylhydrazine,

tide, and 2,3-dichloro naphto-quinone-(L4), but alsoto the preparations from organic mercury compounds.

As the above types of compounds there are to be understood those having the general formula In this formula, R may be hydrogen or a direct additional N-N-bond; R together with X .may be an organic or inorganic radical at the azo or hydrazo group. For instance, R together with X may be linked to the hydraxide radical as CO CS-.-, NH or 50, group. Theradical R may also be linked to the hydrazine radicalvia a methinegroup, like a Schifis base. Furthermore, R and X may be the salt-like radical of a diazloniumsalt or the organic radical of a diazoor diazo- -amino compound. The radical N=(R"), standing in p-position to the above said groupings, is any substituted trivalent nitrogen atom, such as a substituted primary, secondary or tertiary amine, amide, a nitroso compound, or a nitroamine. I k

. Some of the compounds of the aforedescribed type are known, others can be obtained by conventional methods which are illustrated in the following. By oxidation of the quinone oxime acyl hydrazones, which is preferably carried out in glacial acetic acid by means of nitric acid,

for instance acylazophenols result. By reducing the oximes for instance with ammonium sulfide or a mixture of tin II-chloride and hydrochloric acid, the correspondiug acyl derivatives of.p-aminophenylhydrazines are obtained. They canbe further modified at the amino and hydrazino group and oxidised to aminophenylazo compounds. By reaction with aldehydes, benzylidinecompounds result; acyl-cofitpounds are obtained by .the reaction with acid anhydrides or acid chlorides. Besides, ureas, thioureas, isothiocyanates or other derivatives can. beproduced. p y

By reaction of hydrochloric acid or other mineral acids with certain p-aminophenyl-acylhydrazines the salts of p-aminophenyl-hydrazines result; p-aminophenyl-hydrazines however, is also obtainable by other conventional methods. When reacted with aldehydes, it yields benzylidene compounds. I

vBy diazotizing derivatives of p-phenylen'edia'mine, for instance p-aminoacetanilide or p-dimethylaminoaniline, there are obtained diazo'nium compounds which can be stabilized by conventional methods. From these azo compounds, p-amino-phcnylhydrazines substituted in the amino group can be obtained by reduction. Some representatives of the above said classes of compounds are given below by way of illustration, but it is to be understood that the scope of the invention is by no means restricted to the use of these compounds:

Benzoyl-azo-p-nitrosobenzene, chlorobenzoyl-azo-p-nitrosobenzene, benzoyl-azo p nitrosotoluene, p-arninophenylformylhydrazine, p-aminophenylcyanoacetylhydrazine, p aminophenylamino-acetylhydrazine hydrochloride, p-aminophenylaminoacetyl hydrazine hydrochloride, p-aminophenylmethylamino-acetylhydrazine hydrochloride, p-aminophenyl-dimethy1-aminoacetylhydrazine-hydrochloride, paminophenyl trimethylammoniumchloride-acetyl-hydrazine hydrochloride, p-aminophenylpyridiniumchlorideacetyl-hydrazine-hydrochloride, p-aminophenyl-hydroxyacetylhydrazine, p-amino phenyl methoxyacetylhydrazine, p-aminophenyl methylthio acetyl-hydrazine, pa mnophenyl-propionyl-hydrazine, p-aminophenyl-meth oxycarbonylhydrazine, p-a'minophenyl-benzoylhydrazine, p-amjnophenyl-p-aminobenzoybhydrazine, p-aminophenyl-phenylacetylhydrazlne, p-aminophenyl-phenoxyacetyl hydrazine-"pammophenyl dichlorophenoxy-acetylhydrazine, oxalylp-aminophenyl-acetyl-hydrazine,

positions were extended with talcum.

bis-p-amino-phenylhydrazine, malonyl-bis-p-amino-phenylhydrazine, p-aminophenyl-furancarbonylhydrazine, paminophenyl-pyridylcarbonyl-hydrazine, p-aminophenyL semi carbazide, p-aminophenyl-thiosemicarbazide, pamino-phenyl-phenyl- (thio) -semicarbazid, p-aminophenyl-amino-guanidine-dihydrochloride, benzoylazo-p-arninobenzene, chlorobenzoyl-azo-p-aminobenzene, furancarbonyl-azo-p-aminobenzene, acetylaminophenyl benzoylhydrazine, p-nitrobenzylidene aminophenyl-benzoylhydrazine, p-dimethyl-aminobenzylidene-aminophenylbenzoylhydrazine, p-chloro benzylidene-aminophenyl-benzoylhydrazine, p-hydroxy-benzylidene-aminophenyl-benzoylhydrazine, 2 hydroxy-S-chlorobenzylidene-aminophenyl-benzoylhydrazine, 2 'carboxy-benzoylaminophenyl-ethylcarbonic-hydrazine, p-chloro-benzylidene-aminophenyl-formylhydrazine, 2- hydroxy-S-chlorobenzylideneaminophenyl-formylhydrazine, 2-hydroxy-5-chlorobenzy1- idene-aminophenyl-carboxyfurylhydrazine, p-chlorobenzylidene aminophenyl-p chlorophenyl-thioacetyl-hydrazine, v p chlorobenzylidene-aminophenyl ethyl carbonichydrazine, acetylazonitrosobenzene, pheny'lthiosemi-carbazine p methylthiou'rea, phenylthiosemicarbazine pethoxy-phenylthiourea, phenylthiosemicarbazine-p-phenylthiourea, jbenzoylphenylhydrazine p 7 phenylthiour'ea, benzoylphenyl-hydrazine p isothiocyanate, p-arninophenyl-hydrazine-dihydrochloride, p'-aminophenylhydrazine-sulfate, p-arninophenylhydrazine-oxalate, p-aminotolyl-hydrazine-dihydrochloride, benzylidene-aminophenyl acetophenone hydrazine, 4-methoxy-benzylideneaminophenyl-sl-methoxy benzalhydrazone, 4-chlorobenzylidene-aminophenyl-4-chlorobenzal-hydrazone, 2-chlo r0 4 5 hydroxybenzylidene-aminophenyl-Z-chloro-S-hydroxybenzalhydrazone, the sodium salt of p-acetylaminophenyl-diazosulfonic acid, p-acetylaminophenyldi azo-(3-4-dichloro-) benzene sulfonate, p-acetylamino benzene-diazo-cyclotetramethylene-imine, p-a'cetylamino phenyl-hydrazine-hydrochloride, and p-dimethylaminobenzene-diazosulfonic acid etc.

For the purpose of seed disinfection, the above said compounds are applied in the usual manner either as such or after addition of the customary diluents. They may be applied for instance in known manner as fungicidal dusting or sprinkling agent, as dry disinfectant or in solution as wet disinfectant or in suspension as slurry disinfectant. They may also be applied in admixture with other fungicides and/or insecticides and/or substances protecting seed grain from being eaten by birds, or agents improving their solubility. To demonstrate the suitability of the compounds of the invention in the control of plant diseases, the result of experiments is given byway of example in the following tables. The experiments with peas and beets for the control of germination diseases were carried out under conditions which are most unfavorable for the growth of the plants. The germination medium was compost largely infected with phyto-pathogenic fungi.

The experiments were performed in autumn and winter months in a greenhouse which was lighted only with natural day-light and in which temperatures of 10-15 C. prevailed. Such conditions impair the power of resistance of the seedlings and promote infection;

The preparations were applied as dry disinfectants at the concentrations indicated in the examples. The com v 7 Instead of talcum, bentonite, chalk, clay, kieselguhr etc. may be used as carrier.

-' of formulations containing [2 g. of] the activ'esubstances I per '1 kg. of seed and, in the case "of sugar beets, with 6 2. 1m kg. of seed.

These proportions, however, may be varied within admwide limits; say from 05-10 g. per kg. of seed; in r 1 name cases, still lower or higher quantities may be used.

Under the heading healthy plants or, in relation to beets, healthy plants" and healthy shooting-up'spots, 1 the number of the healthy shooting-up spots --observed after 4 weeks is indicated in percent referred to 100 seeds.

EXAMPLE! Experiments with polyembryonate sugar beetseed I 7 man:

QM!- M eungt, er 1N bllll. m- 'plled lettnlubehna "an. mm: 7

' 5'0: wt hum,

can

led lam IND find 82 B rall in ame 2.2 0 on in H;NC-NH-NH NHa+ n01 u e 14 ua Und 4: so Phenyl-Hg-aeetn I l. 2 6 68 113 mNCNHNH-ONH1+HC1 a r a m mN-Q-NH-NHQNE +'Hc1 2.5 eas no Undresse I4 82 Phenyl-Hg-eeetate 2.2 o 3 Q2 CHI-N l c-Nn-NH-O-Nn, H01 15 a so u:

Ha-N 7 EXAMPLEZ Experiments with peas (Aldermann peas) eonnanhealthy eentyn plant! mplied n arm-4 active substance don. mm! week: perperl Invencent kgml ant seed Und 1a Ph nyl-Hg-nmhfln l 2. 2 2 89 Cm-s-cmcomz-nfi-Onm 1a a u cm-s-cmcoNH-NnO-NH, a 2 u Undress 28 Phenyl-Hg- 2. 2 2 I0 I (BIOS-CECONH-NHONH; as a at EXAMPLE 3 Tilletia tritici-epore germination test by the Gassner method quantity coneenapplied eettvembatlnee tratlon, In gram: spore germination percent perm.

of t

Undr-r 7 Complete.

co-Nn-Nn-O-NH, cm-cnl-cm-c u 1 Nll.

00-NHNHONHa EXAMPLE 3 -,Continued eoncenapplied native substance tration In grams spore germination percent per 1 kg.

of seed W 1 C-NH-NH NH,

1 A few spores here md than. pp-nn-nnO-nm 01-05-0310 oNn-Nn-O-Nm an 1 Nu.

N- CoNn- -Nn-Nm 1 Do. m 1 H|C\ /N O CONH VNH-ONH| 1o 1 Afaw spoma. H10 1 EXAMPLE 4 Experiment with pe'as (Aldermann peas) (spotted, non-picked peas) qunntl hea'thy concenapplle plant; the lublhnm nation, in grams after 4 percent per] kg. week: In

ofsead percent Undnm 6 PhonyI-H. p v I 22 2 m OaHr-D-E-NH-NHONE +1101 115 2 -QkO-C -Nflwhffl NH; H0] 5 2 53 EXAMPLE 5 Experiment with peas with polyembryonate active mhctanoe (Aldermann peas) sugar beet seed .concenhealthy healthy healthy tratlon, plants shootlngplants percent up spots Undress 3 26 47 Phenyl-Hg-w m e 2- 15 52 1 6 63 49 99 C ONH-NH NH0 0 CH1 15 80 69 165 143 w W CH: 6a O a V 15 01 159 at!" mbstanm Undnu lhanyl-Hgmtato...

mm a m m m a m mm mm H m nu ma E mm mm mm m m n A. w M? EXAMPLE 7 m mm m msm m v mm. h 7' t mm A M W W m 3mm mum m a u m a an mm) m hmw mt m E w m 5 m mmw x m T m m m m m m Tl .w m M m m m m m u H m .m m m m m m m m h m m w M. n n m 1 L mm qw m m;

v c c c m m m 4 u no J J M E m m m mm EXAMPLE 8 Experiment with peasLUderwith polyemhryoactive substance" mann peas) nate sugar beet seedv coneenhealthy healthy healthy tratlpn, plants shootingplants percent up spots Undresse r I 17 Phenyl-Hg 2.2 80

C.H;CNHNHC.Hap-N=C=S 25 5 69 1 10.0 7o 7 E (limo-C11100NHNH-C|H4-N=OHCsH4pClL &3 l I};

I Hg. To compare with the activity of the cmpounds accord ing to the invention, the number of the shooting-up spots of undressed seed and the number of the sheoting-up spots of seed dressed with a mercury disinfectant are given in the above tables.

EXAMPLE 9" Experiment with peas withpolyeinr (Aldermenn brynnate sugar active substance peas) beet seed concenhealthy healthy healthy tratlnn. plants shooting plants percent up spots Undressed 2 4 a Phenyl-H. 22 46 40 76 1 65 5 87 15 89 36 91 50 43 84 =NNHCsH4.N=CH-C.H

cmo-O-c11-N-NH-c.rr.-N=cn-c.m- -oon. 1a 57 23 as 50 76 28 58 t 5 e1 l-p--C.H-0H=N-NHQHaN=OE-C Cl 15 75 42 79 50 80 45 87 OH OK i t 'CH=NNHC H|N=CH EXAMPLE 10 1 healthy plants after 4 weeks referred I eoneento 100 peas or 100 pulyembryonate No. active substance tratlon sugar beet balls in per cent peas beet peas peas peas peas Undressed- 9 104 9 0 2 6 Phenyl-Hg-ace'tats- 2.2 39 137 65 43 24 32 5 onto 0 NH N=N+S 0001 us 26 50 51 CH CH v P a 142 CHCONH N=N 15 63 156 I 64 138 CHI- Ha s 25 CH;CONH"' "'N=N'Cl+2n0h 15 39 A dry disinfectant consisting of 5% p-aminophenylhydrazine hydrochloride and 95% of talcum was applied in the usual manner to sugar beet seed in a quantity of 6 g. per 1 kg. of seed. For comparison, the seed thus treated and undressed seed and seed treated with a dry disinfectant containing 2.2% Hg in the form of phenyl- Hg-acetate were sown at the same time. The seeds were sown in wooden boxes in ordinary compost infected with phytopathogenic organisms and cultivation was carried out in the greenhouse at temperatures varying between 10 and C. The untreated seed produced 58 healthy plants from 100 beet balls after 31 days, whereas 128 healthy plants were obtained from the seed treated with the mercury disinfectant. As compared therewith, the seed treated with the disinfectant containing p-aminophenylhydrazine-chlorohydrate produced 163 healthy plants. The application of this disinfectant did not show any depression of germination even when applied at a concentration of 50%.

We claim:

1. A fungicidal composition containing as an active ingredient 0.5-50% of a p-aminoarylazo compound of the general formula in which R is a radical selected from the group consisting of 820 and hydrazo; X is a member selected from gredient is oN-O-Ndt-c 0-CIHI 3. composition of claim 1 wherein the active ingredient is 7 EXAMPLE IO-Continued hcialtllioyo plants altar; 4 vlvneksbrreferreg D98! 0 No. active substance l r tlh h saga: beet balls poyem you in perpeas beet pea peas peas peas 5 51 }CH:OONH N=NB0;K 15 so so 01 s 46 }HCONHON=NCI+ZI1GI, 15 as so as a re C0N=N NH, 1s 72 so 02 at 0.: 4s m l 1 as s 7a CH: :4 a as as N- N=NS OINS 15 77 as so so 01 g i mIIZIIIIII fO C1 60 so EXAMPLE 11 4. A composition of claim 1 wherein the active ingredient is [5. A process for controlling fungi which comprises applying to seed a fungicidal composition of claim 1.]

[6. The method of claim 5 wherein the active ingredient corresponds to the following structural formula [7. The method of claim 5 wherein the active ingredient corresponds to the following structural formula [8.The method of claim 5 wherein the active ingredient corresponds to the following structural formula NON=N-BOsNaI HaC 9. A process for controlling fungi which comprises applying to seed a p-aminoorylazo compound of the general formula 11. The process of claim 9 wherein the p-ominoatylaao compound corresponds to the following structural References-Cited in the file of this patent formula: I or the original patent EN "NH'NHCO'C6HJ UNITED STATES PATENTS 5 2,054,062 Bonra'th Sept. 15, 1936 12. The process of clazm 9 wherem the p ammourylazo 2,673,197 Jensch Mar. 23) 1954 compound corresponds to the following structural formula:

MHM 10 11:0 7 

